Imidazoline derivatives and process



United States Patent IMIDAZOLINE DERIVATIVES AND rnocrss Hans S. Mannheimer, New York, N. Y., assignor to John J. McCabe, Jr., and Hans S. Mannheimer, as joint venturers No Drawing. Application March 26, 1956, Serial N0. 573,654

13 Claims. (Cl. 260309.6)

This invention relates to novel compositions and to methods for producing them. In one of its more specific aspects, the invention is directed to novel derivatives of that class of components which may be prepared by following the methods described in my copending application, Serial No. 521,393, filed July 11, 1955, and having the following general Formula I:

in which R is a hydrocarbon radical of 4-18 carbon atoms; R2 is selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms, (1)) hydroxy substituted hydrocarbon groups of 1-4 carbon atoms, aliphatic ether groups, each of said groups having a single ether linkage therein and otherwise being hydrocarbon of 24 carbon atoms, (d) aliphatic ether groups, each of said groups having a single ether linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (f) aliphatic 'keto groups, each of said groups having a single keto linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms; M is an alkali metal and preferably sodium or potassium which are obvious equivalents.

Said compounds of Formula I may be derived from the metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates, examples of which are disclosed in my U. S. Patent 2,528,378, and which I'shall hereinafterrefer to as cycloimidates. Said cycloimidates having the following general formula:

R, R2 and M have heretofore been defined. The methods for producing said cycloimidates and illustrative examples of a number of said cycloimidates are all of the cycloimidates disclosed in said patent which is made part hereof.

One of the methods described in said patent for the production of said cycloimidates 'is to first produce a cycloimidine 'by reacting .one mole of a monocarboxylic acid, having at least 4 and preferably 4-18 carbon atoms in its radical connected to its COOH group, with one mole of aminoethylethanolamina'known in said patent and herein as reactant A. Then one mole of said cycloimidine is reacted with one mole of a monohalocarboxylic acid, such as monochloracetic acid, monochlorpropionic acid, monochlorlactic acid, etc., in the presence of a fixed proportion of caustic soda, all described in said patent, to produce said cycloimidates. Such cycloimidates are produced because of the marked preferential of the reactants and because of the mole proportion of reactants being one to one.

As disclosed in my application 521,393, said cycloimidates, under certain controlled conditions, may be reacted with one of said monohalocarboxylic acids to replace the metallic element M of the R2-OM group thereof with an R2-COOM group:

Still another method which may be employed to pro duce said compounds of Formula I is to heat together at approximately C. one mole proportion of said cycloirnidine and an aqueous solution at a pH of about 13 produced by previously combining at a temperature no greater than 20 C. 2 moles of said monohalocarboxylic acids, having 1-4 carbon atoms in its hydroxy substituted hydrocarbon group, such as CHzCHOH or in its unsubstituted hydrocarbon group, such as CH2, C2H4, CsHc, C4H8, and approximately 4.5-5 moles of caustic soda. The mass is maintained at said temperature of approximately 100 C. until the pH thereof decreases to the range of approximately 8.8-9.3.

The following are illustrative examples given merely for the purpose of specifically illustrating how some of the compounds of Formula I may be produced, all parts being given by weight unless otherwise specified:

Example A 200 parts of lauric acid and 104 parts of reactant A are placed in a reacting vessel and are heated sumciently to melt the lauric acid whereupon an agitator located therein is started and mixes and maintains these components in mixed condition. While being constantly agitated the mix is heated under vacuum of about mm. pressure for about 3 hours while gradually raising the temperature to C. During this period 18 parts of water have been distilled ofi. Then the temperature of the entire mass is gradually raised to 220 C. over a period of about 2 hours while the mercury pressure has been decreased to a value no greater than 30 mm. Under these conditions 18 more parts of water are distilled off leaving behind in the reaction mass at 100% pure product which is a disubstituted cycloimidine. which is a light colored viscous liquid at room temperature. Then this reaction product is allowed to cool to room temperature and the entire mass is added to a previously prepared solution produced by adding 192 parts of monochloracetic acid and 180 parts of caustic soda to 600 parts of water. This solution was prepared and maintained at a temperature below 20 C. before the addition of said disubstituted cycloimidine. This mixture is heated to 100 C. and maintained at this temperature for 2 hours. During this period the pH of the mix is reduced from approximately 13 to 8.8-9.3. At the end of this period the pH of this mass is no longer subject to change by continued heating at said temperature and a sample of the resultant product is water soluble to a sparkling clear solution. At the end of this period the mass consists chiefly of a water solution of a compound hereinafter known as Product A and having the following formula:

OH 7 Example A-] 200 parts of lauric acid and 104 parts of reactant A are placed in a reacting vessel and are heated sufliciently to melt the lauric acid whereupon an agitator located therein is started and mixes and maintains these components in mixed condition. While being constantly agitated the mix is heated under vacuum of about 110 mm. pressure for about 3 hours While gradually raising the temperature to 170 C. During this period 18 parts of water have been distilled off. Then the temperature of the entire mass is gradually raised to 220 C. over a period of about 2 hours while the mercury pressure has been decreased to a value no greater than 30 mm. Under these conditions 18 more parts of water are distilled off leaving behind in the reaction mass a 100% pure product which is a disubstituted cycloimidine which is a light colored viscous liquid at room temperature. Then this reaction product is allowed to cool to room temperature and the entire mass is added to a previously prepared solution produced by adding 96 parts of monochloroacetic acid and 90 parts of caustic soda to 300 parts of water. This solution was prepared and maintained at a temperature below C. before the addition of said disubstituted cycloimidine. This mixture is heated to 95 C. and maintained at this temperature for 2 hours. During this period the pH of the mix is reduced from approximately 13 to 8-8.5. At the end of this period the pH of this mass is no longer subject to change by continued heating at said temperature and a sample of the resulting prdouct is water-soluble to a sparkling clear solution which clouds upon standing. Then to said reaction mass there is added additional parts of caustic soda dissolved in 21 parts of water and heating is continued to maintain said mass at about 95 C. for an additional 1 hour.

At the end of that period said mass, known as mass X, is cooled to room temperature and then there is added thereto a previously prepared solution produced by adding 96 parts of monochloroacetic acid and 80 parts of caustic soda into 300 parts of water while maintaining same at a temperature no greater than 20 C. and preferably at about 15 C. The resultant mixture of said mass and said solution is then heated to and maintained at about 100 C. for about 1-2 hours. In that period, the pH of the resultant product will have been reduced from approximately 13, that of the original mixture, to approximately 8.8-9.3. Then the resultant product is cooled to room temperature and consists chiefly of an aqueous solution of a reaction product, identical with that of Example A, with the amount of water in said solution being slightly greater than that of the solution thereof in Example A.

Example B All of mass X of Example A-l may be cooled to room temperature and there is then added thereto a solution consisting of parts of caustic soda dissolved in 40 parts of water. Then to said mixture there are added 80.5 parts of chlorhydrin. This mixture is heated over a period of 1 hour to 95 C. The mass is subsequently maintained at this temperature of 95 C. until there is no change in pH, this taking approximately 2 to 3 hours.

The resultant mass is then cooled to room temperature and mixed with a previously prepared solution produced by changing 96 parts of monochloracetic acid and 80 parts of caustic soda into 300 parts of water while being maintained at about 15 C. The mixture is then heated to and maintained at about 100 C. for 1-2 hours. At the end of this period the mass consists chiefly of an aqueous solution of a compound hereinafter known as product B and having the following formula:

N CH:

l 02Hl-O-C2H4OCHr-GOON8.

CnHar- -N CHr-COONa Example C 172 parts of capric acid and 104 parts of reactant A are heated and reacted under the same condition as given in Example A, and 240 parts of the disubstituted cycloimidine produced thereby are introduced into a solution of 220 parts of monochlorpropionic acid and 190 parts of caustic soda in 500 parts of water prepared'and maintained below 20 C. The resulting mixture is then heated under the same conditions as outlined in Example A until the resulting product forms sparkling clear aqueous solutions and is no longer subject to pH change in continued heating. The mass consists chiefly of an aqueous solution of a compound hereinafter known as product C and having the following formula:

282 parts linseed fatty acid and 104 parts reactant A are treated in the same manner as described in Example A. The entire reaction product is then processed with an aqueous solution of 192 parts monochloracetic acid and parts of caustic soda previously made and maintained below 20 C. and subsequently processed in the manner of Example A to produce reaction product hereinafter known as product D and having the same formula as that of Example A, except that CrzHar is substituted for CnHza therein.

Example E 116 parts of caproic acid and 104 parts of reactant A are condensed in the manner as described in the previous examples and the resulting reaction product is subsequently processed in the same manner as that set forth in the processing of the disubstituted cycloimidine of Example D. The reaction product is hereinafter known as product E and has the same formula as that of Example A, except that CsHs is substituted for C11H23 therein.

Example F 284 parts of stearic acid and 104 parts of reactant A are heated in the like manner as described in previous ex amples, and the resulting reaction product is then introduced into an aqueous solution of 220 parts monochlorpropionic acid and parts of caustic soda. The process is carried out in the same manner as described in the previous Example A and there is produced a product hereinafter known as product F and having the same formula as that of Example C, except that CmHas is substituted for C9H19 therein.

Example G 290 parts dodecyl benzoic acid and 104 parts of reactant A are condensed in the manner described in Example D and the resultant product is processed in the manner of Example D wherein there is produced a compound hereinafter known as Product G and having the same formula as that of Example A, except that C12H25C8H4 is substituted for CnHzs therein.

1 Example H 228 parts of myristic acid and 104 parts reactant A are reacted in the manner described in Example D and the resultant product is processed in the manner of Example D whereby there is produced a novel compound having the same formula as that of Example A, except that C13H2'1 is substituted for CnHzs therein.

Examples I-M One mole proportion of the respective cycloimidates described in Examples 10-14 of said Patent 2,528,378 are mixed with aqueous solution prepared at 18 C. by the addition of 1 mole proportion of monochloracetic acid and about 2 moles proportion of caustic sod-a in about 30 moles of water and such mixtures are maintained atabout 100 C. for approximately 2 hours whereupon the pH thereof decreases from 13 to about 8.8 9.3 to provide compounds which are the same as those of Examples 10-14 of said patent except that the sodium atom of the RONa groups thereofare replaced by and an illustrative example of this is such group of Example 10 having its sodium atom so replaced to become CHzCHOHCI-IzOCHzCOONa.

A large number of other specific compounds may be producedby using starting compounds other than those defined in any of the aforesaid examples and differing therefrom in the radical R. Also other specific compounds may be produced by using a monhalocarboxylic acid other than the specific ones employed in the aforesaid examples.

Prior to this invention, it was known that cationic surface active agents and anionic surface active agents when together in aqueous solution resulted in the production or formation of water-insoluble compounds; and that adding an anionic surface'active agent to an aqueous solution of another anionic surface active agent resulted in a mere physical combination of said agents and that no reaction would occur between them.

Said compounds of Formula I normally behave anionically in aqueous solutions having a pH above 7, and consequently it was expected that wheniri aqueous solution together withanionic surface I agents that .they would be combined physically only and that no other reaction would occur therebetween. In'the course of my experimentations, I have discovered that said compounds of Formula I could be reacted with. certain anionic surface active agents at a pH above? to produce Water-soluble reaction products. Not only did I make said discovery, but I further discovered that water solutions of such reaction products had viscosities greater than corresponding aqueous solutions of the compounds of Formula I and also exhibitedbetter foaming characteristics than did said compounds of Formula I in very low dilutions under extreme water hardness conditions. Said reaction products are non-toxic and non-irritating to the human skin. They have been found eminently useful as general utility detergents, such asforcar washing, dish washing, clothes washing, etc.

According to this invention, one or a combination of two or more of said compounds of Formula I of the general structural Formula 1 are reacted with one or a combination of two or moreanionic surface active agents of the following general structural Formula II to provide novel, water-soluble compounds having the following general structural Formula HI, and having high wetting, detergeucy and surface active properties and capable of providing voluminous and stable-foams in aqueous solutions, and which aqueous solutions are substantially nonirritating to the skin and eyesof normal human beings.

U FORMULA n Ra- -z c2H4o --so3- M AFORMULAVIIII /O I\I2 N V cm 7 A R2-.-O--Ra -OOOM I k III-DOOM:

aha-(canto), q;

wherein R3 is a hydrocarbon radical, generally aliphatic or aliphatic-aromatic, and having at least 6 carbon atoms and for most purposes 6-20 carbon atoms; Z is either oxygen or sulphur; and x is an integer and being at least 1 and generally l-S, and preferably 3; M, R, and R2 have heretofore been defined in Formula I.

According to this invention, I react a compound of Formula I with a compound of Formula II to provide the novel and highly useful compounds of Formula III. In general this reaction is carried out in a solution containing compounds I and II and to which a quantity of an acidic agent such as a strong mineral acid, as for example hydrochloric, sulphuric or its equivalent has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approximately -200 F. In this reaction under the aforesaid conditions, compounds of Formula III are produced and have high water solubility despite the fact that R3 has 6 or more carbon atoms. Such compounds of Formula III have unexpectedly high water solubility, while the corresponding salts of cationic compounds are water insoluble. The resultant solution can be used directly as a surface active agent, wetting agent or detergent for the purposes indicated for the cycloimidates. While the quantities of the compound of Formula I and compound of Formula II may be equimolecular for good yield of compounds of Formula III, I may employ an excess of either and in general the mole ratio for compound of Formula I to compound of Formula H may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out an aspect of this invention is to first dissolve a compound of Formula I in water and then the pH thereof is adjusted to approximately 12-13 (measured electrically) by the addition of aqueous caustic soda if required. The temperature of said solution is raised to 100-200 F. and preferably in factory practice to F. Then a quantity of a compound of Formula II is dissolved in water in a separate container and this solution is added to said first solution and the mass is maintained in said temperature range While being constantly stirred and an acidic agent is added thereto to reduce the pH thereof to a value below 10 and in the range of approximately 7 to 9, and preferably of approximately 8.2 to approximately 8.7. At the end of the acidic agent addition, the stirring is continued and the temperature of the mass maintained for about 10-20 minutes after which the solution is allowed to cool and is a finished product.

The following are specific examples merely given by Way of illustrating the invention and are not to be taken by way of limitation, all parts being given by weight unless otherwise specified.

Example 1 An aqueous solution of 480 parts of product A in 720 parts of water is heated approximately 140 F. and its pH adjusted to 12-13 (measured electrically) by the addition of aqueous caustic soda. While being constantly stirred and maintained at that temperature there is added a solution of 400 parts of sodium'salt of lauryldiethoxyether sulfate:

in 600 parts of water. Then while stirring and temperature is maintained there is added thereto between about 30-40 parts of hydrochloric acid solution (32%) whereby the pH of the mass is lowered to a value in the range of 8.2 to 8.7.. Stirring is continued and the temperature maintained for about 10 minutes more. The resultant alae'nsee product is a solution of the novel reaction product having thefollowingformula:

N CH: l CaH4-OCH2-COONa CnHsr- N\ OHgCOONu C17H25-O(C2H4O) S()a Example 2 Employ the same procedure and components as set forth. in Example 1 except that only 200 parts of the lauryl'diethoxyether sulfate are used. In this instance the resultant product is a solution of the reaction product whose structural formula is shown in Example 1 together with unreacted Product A used, in the approximate proportion of 2 parts of the former to 1 of the latter.

Employ the same procedure as that set forth in Example 1, 'but employ the components indicated in the following Examples 3-18; the quantity of hydrochloric acid solution (32%) is variable to lower the pH to values indicated in Example 1 to obtain the reaction products of said Examples 3-18.

Example 3 480 parts of product A in 720 parts of water. 250 parts of octylmonoethoxyether sulfate sodium salt:

CsHn-O C2H4O -SO3Na in 400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT /CE2 N CH2 (1/ l/G2H4-O-CHr-C OONa cn ar- ""N CHr-COONB CsH1r-O(CzH;O)-$Oa Example 4 I 450 parts of product C in 800 parts of water. parts of tridecyltetraethoxyether sulfate sodium salt:

C13H27-O(C2H4O)4-SO3-Na FORMULA OF NOVEL REACTION PRODUCT /Og2 N CH2 525 parts of product B in 950 parts of water. 500 parts of nonylphenoltriethoxy ether sulfate sodium salt:

FORMULA OF NOVEL REACTION PRODUCT N/ \CH2 l I/CzH4-O-CzH4OCHg-C OONu uHra- -N CHz-C o ONa OoH wol14-O (OzH40)s-S Os V Example 6 480 parts of product A in 720 parts of water. 250 parts of hexylmonoethoxy thioether sulfate sodium salt:

CeH1s-S-(C2H4O) -SO3---N'a in 400 parts of water.

masts or uovnr, imacrion mam" UH, p 'N OHs V I O:H4-O-OHa-OOONB Ox1HaO --N/ v OHsOOONa CsHrrS-(OsHdU-SOI Example 7 600 parts of product F dissolved in 900 parts of water. 600 parts stearoylpentaethoxythioether sulfate sodium in 900 parts of water.

FORMULA OF NOVEL REACTION PRODUCT I C 2 N OHa o,Hi0-oHT-co0Nn C17Has-C---N CaHr-OOOku CnHas-- -(C2HiO)sSOa Example 8 525 parts of product H dissolved in 800 parts of water. 350 parts of octylpheuol diethoxy thioether sulfate potassium salt:

FORMULA OF NOVEL REACTION PRODUCT OnHw- ----N Example 9 480 parts of product A in 720 parts of water. 400 parts of decyltriethoxy thioether sulfate sodium salt:

4 parts-of product A in 720 parts of water. 500 parts of amylphenylpentaethoxy ether sulfate sodium salt:

FORMULA OF NOVEL REACTION PRODUCT OH: N \OHI I 0:34-0-0111-0 0 ON; Cums-O N OKs-O 0 ONE 9 p Examples 11-18 Employing the same procedure as that set forth in Example 1, but using 1 mole of products D, E, G, I, J, K, L, and M respectively and 1 mole of the sodium salt of lauroyl monoethanolamide sulfate, there are produced 8 other novel compounds, which differ from the novel reaction product of Example 1 in either R or R2 or both.

It is also to be understood that any of the products AM, which are shown herein merely as illustrative examples of the starting materials of Formula I may be reacted with any of the specific sulfate or sulfonate salts which are shown herein merely as illustrative examples of reactants of Formula II to produce novel compounds of Formula III.

It is to be understood that the use of Na in the specification and claims is meant to indicate any of the other alkali metals because of their obvious equivalency.

It is also to be understood that instead of first adjusting the pH of the compound of Formula I to 12-13 before the addition of the compound of Formula II, any other method may be employed to obtain the condition whereby the pH of the solution of I and II is at least and preferably l0.5-1l before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approximately 9. For example, I and II may be dissolved together and this solution may by the addition of caustic soda when required have its'pH adjusted to at least 10, and then at 100-200 F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution at pH at least 10 is brought to a temperature in the range of l0O200 F.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all the geenric and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

I claim:

1. A novel compound of the following formula:

in which R is a hydrocarbon radical of 4-18 carbon atoms; R2 is selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms, (b) hydroxy substituted hydrocarbon groups of 1-4 carbon atoms, (0)

aliphatic ether groups, each of said groups having a single ether linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ether groups, each of said groups having a single ether linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being bydrocarbon of 2-4 carbon atoms, (f) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms; R3 is selected from the class of aliphatic and aliphatic-aromatic hydrocarbon radicals of 6- 18 carbon atoms; Z is selected from the class of oxygen and sulfur; x is 1-5; and M is an alkali metal.

2. A novel compound of the following formula:.:-

in which R is a hydrocarbon radical of 4-18 carbon atoms; R3 is hydrocarbon of -6-20 carbon atoms; and x is l-S.

3. A novel compound of the following formula:

Ra is hydrocarbon of 6-20 carbon atoms; and x is l-5.

4. A novel compound of the following formula:

in which R3 is a hydrocarbon radical of 6-20 carbon atoms; and x is l-S.

5. A novel compound of the following formula:

in which Ra is a hydrocarbon radical of 6-20 carbon atoms; and x is 1-5.

6. A novel compound of the following formula:

in which x is 1-5.

7. A novel compound of the following formula:

in which at is 1-5.

8. The method comprising under pH conditions of apseamen a 11 proximately 710 approximately 9 reacting with each other compounds of the following Formulas I and II:

FORMULA 'I OH: N/ CHa l l Rr-O-Rr-COOM R-c---N R:- C O 0 M H FORMULA II being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (a) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (f) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms; M is an alkali metal; R3 is selected from '12 the class consisting of aliphatic and aliphatic-aromatic hydrocarbon radicals of 6.- -2 0 carbon at ms; Z is Selected from the class consisting of oxygen and sulphur; and x is 1 -5- '9. The method comprising to a solution containing a compound of Formula I and a compound of Formula II both defined in claim 8, adding a quantity of an acidic agent to lower the pH thereof to a value of approximately 7 to approximately 9 and maintaining the temperature of the mass between about 100 F. and 200 F.

10. The method comprising to a solution whose pH is at least 10 and containing a compound of Formula I and a compound of Formula 11 both defined in claim 8, adding a quantity of an acidic agent to lower the pH thereof to a value of approximately 7 to approximately 9 and maintaining the temperature of the mass between about 100 F. and 200 F.

11. The method defined in claim 8, with the mole ratio of compound of Formula -I to compound of Formula II being 2 moles of the former to 13 moles of the latter.

12. The method defined in claim 9, with the mole ratio of compound of Formula I to compound of Formula II being Zmoles of the former to 1-3 moles of the latter.

13. The method defined in claim 10, with the mole ratio of compound of Formula I to compound of Formula II being 2 moles of the former to 1-3 moles of the latter.

No references cited. 

1. A NOVEL COMPOUND OF THE FOLLOWING FORMULA: 